CN110511348A - A kind of thermosetting resin cured matter and preparation method thereof of the tool electric conductivity of softness - Google Patents

A kind of thermosetting resin cured matter and preparation method thereof of the tool electric conductivity of softness Download PDF

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Publication number
CN110511348A
CN110511348A CN201910742492.4A CN201910742492A CN110511348A CN 110511348 A CN110511348 A CN 110511348A CN 201910742492 A CN201910742492 A CN 201910742492A CN 110511348 A CN110511348 A CN 110511348A
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China
Prior art keywords
thermosetting resin
resin cured
electric conductivity
cured matter
agent
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Chinese (zh)
Inventor
严兵
赵清新
郎鸣华
何定军
于洋
刘圣强
刘腾达
郭海军
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Jiangsu Aosheng Composite Materials Hi-tech Co Ltd
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Jiangsu Aosheng Composite Materials Hi-tech Co Ltd
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Priority to CN201910742492.4A priority Critical patent/CN110511348A/en
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
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    • C08J9/0085—Use of fibrous compounding ingredients
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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  • Health & Medical Sciences (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a kind of thermosetting resin cured matter, contains 100 parts by weight of urethane cures object；10~30 parts by weight of carbon fiber powder fiber；And there is porous structure, porosity is 10~80%.Thermosetting resin cured matter of the present invention, combine the excellent electric conductivity of carbon fiber powder fiber and the excellent flexibility and elasticity of urethane cures object, by controlling porous structure, solidfied material is further improved, so that thermosetting resin cured matter is more soft, has lasting electric conductivity.

Description

A kind of thermosetting resin cured matter and preparation method thereof of the tool electric conductivity of softness
Technical field
The present invention relates to Material Fields, and in particular to a kind of thermosetting resin cured matter of the tool electric conductivity of softness.
Background technique
After metal material is powered, thermal energy can be generated.Using this phenomenon, metal material can be used as thermo electric material, be used for Heat preservation, heating.But at work due to metal electric heating material, Yi Fasheng oxidation reaction and go bad, fail, can also generate light Radiation leads to energy loss.Carbon material, such as carbon fiber, carbon black, graphite, graphene, carbon nanotube have certain conduction Property, it can be mixed with resin, conductive plastics is made, be used for such as film heating electrode slice, electric heating sheets, electricity instead of metal material The fields such as hotting mask.
In actual use, it is sometimes desirable to above-mentioned conductive exothermal material be it is soft, can deform to a certain extent simultaneously Keep the ability of conductive fever.At this point, often using elastomer as resin matrix
Carbon material is easy aggregation in resin matrix, and concentrating portions are more easily damaged as starting point, matrix.It is difficult in the base To form conductive network, thus it is unable to get sufficient electric conductivity.It, can if largely adding carbon material in order to improve electric conductivity Cause the decline of elastic body soft.Therefore, flexibility and electric conductivity in order to balance, need to divide carbon material as homogeneously as possible It dissipates in matrix.
In order to improve the dispersibility of carbon material, what CN201280034136.3 was proposed using a kind of containing acrylic resin Copolymer, or mixtures thereof acrylic resin, polyurethane resin containing this analog copolymer can be improved the dispersibility of carbon material. But acrylic resin has certain smell, is not suitable as articles for daily use.
It is poly- that CN201810149769.8 provides a kind of graphene containing anionic dispersing agent or high-molecular type dispersing agent Urethane film, dispersing agent facilitates the dispersion of carbon material, but can cause to have an impact to the mechanical property of material.Point of poor compatibility Powder is possible to that material surface can be exuded to.
So the prior art is difficult to prepare a kind of softness, the material of electric conductivity can be deformed and kept.
Summary of the invention
The present invention provides a kind of thermosetting resin cured matter for having electric conductivity, and material is soft, and conductive material is in matrix In be uniformly dispersed, can be deformed to a certain extent and keep electric conductivity.Specifically, the present invention provide it is a kind of softness Have the thermosetting resin cured matter of electric conductivity, contains: 100 parts by weight of urethane cures object；10~30 weight of carbon fiber powder fiber Measure part；And there is porous structure, porosity is 10~80%.
Urethane cures object is the cross-linked polymer containing carbamate groups in repetitive unit, can be by polyester, poly- Ether or urethane oligomer are copolymerized to obtain with binary or multicomponent isocyanate.Polyurethane can be adjusted by control copolymerization component The mechanical property of solidfied material.
Thermosetting resin cured matter of the present invention has the effect that containing porous structure in the thermosetting property Emptying aperture is introduced in resin cured matter, can reduce the tree between emptying aperture in reducing material while the relative volume ratio of resin The thickness of rouge wall.Since carbon fiber powder fiber is distributed only in resin, the resin wall thickness between emptying aperture reduces so that carbon fiber Dimension powder fiber is more likely formed conductive network, to improve electric conductivity.Another effect of porous structure is to improve thermosetting property The flexibility of resin cured matter.
Based on the above effect, the porous structure of the thermosetting resin cured matter should have 10~80% hole Rate.Porosity is too low, it is difficult to achieve the effect that above-mentioned reduction resin wall thickness；Porosity is too high, then resin wall thickness may It is too small, it is mismatched with the size of carbon fiber powder fiber, also is unfavorable for forming conductive network.Preferably, the porosity is 20~70%, further preferred 30~60%.
Further, preferably of the present invention in order to improve the electric conductivity of thermosetting resin cured matter of the present invention Thermosetting resin cured matter average pore size be 1~100 micron.The pore structure of features above is between the resin wall thickness reducing hole Degree, the comprehensive mechanical property for promoting thermosetting resin cured matter, including intensity and toughness have significant effect.Average pore size is small When 1 micron, electric conductivity is bad；When average pore size is greater than 100 microns, electric conductivity is also bad, and will cause the drop of mechanical property It is low.
With no restrictions, but pore-size distribution is smaller for the pore-size distribution in the hole, and the various performances such as electric conductivity, mechanical property are got over Uniform, preferably small-bore is distributed, for example pore-size distribution is less than 1.5.
In order to improve the flexibility and elasticity of the urethane cures object, while certain mechanical property is kept, into one Step, urethane cures object of the present invention contains aromatic polyester segment and aliphatic polyether segment.Further, described Aromatic polyester segment include polyphenyl dioctyl phthalate ethylene glycol segment, polyethylene naphthalate segment, poly- biphenyl dicarboxylic acid One of glycol ester segment is a variety of.The aliphatic polyether segment include polyethylene glycol segment, polypropylene glycol segment, One of polytetramethylene glycol segment, poly- hexylene glycol segment are a variety of.
Carbon fiber powder fiber as carbon fiber filament it is ground made of micron order fibre reinforced materials, structure and performance It is determined by carbon fiber filament, by its source point, it is fine that polyacrylonitrile-based carbon fibre powder fiber, asphalt base carbon fiber powder can be divided into Dimension, viscose-based carbon fiber powder fiber, phenolic aldehyde base carbon fibre powder fiber and its modified product.With other materials such as carbon fiber filament Material is compared, have shape is tiny, surface is pure, large specific surface area, be easy to by resin wetted, be uniformly dispersed, feeding manner multiplicity, The spies such as simple process.In the present invention, carbon fiber powder fiber is used to assign thermosetting resin cured matter of the invention with electric conductivity. Relative to conductive materials such as other carbon materials, carbon fiber powder fiber is easier in urethane cures object of the present invention Conductive network is formed, and in thermosetting resin cured matter of the present invention deformation, conductive network is still had, and has and leads Electrically.By urethane cures object be 100 parts by weight in terms of, the carbon fiber powder fiber is preferably 15~25 parts by weight.Carbon fiber When tieing up powder fiber too high levels, it may occur that reunite, to influence electric conductivity.
Further, thermosetting resin cured matter of the present invention, also contains conductive auxiliary agent, and the conductive agent that helps is One of conductive black, carbon nanotube, graphite are a variety of.Conductive auxiliary agent is for assisting carbon fiber powder fiber solid in polyurethane Conductive network is formed in compound matrix, and in thermosetting resin cured matter of the present invention deformation, for remaining conductive Network still has.
Further, in terms of by urethane cures object for 100 parts by weight, the conductive auxiliary agent is 5~15 parts by weight.
Thermosetting resin cured matter of the present invention can be prepared by well known method.It is preferable to use following methods systems Preparation Method contains following steps: raw material needed for obtaining after host agent, carbon fiber powder fiber, curing agent, foaming agent are mixed, Yu Yi Determine to be formed by curing cross-linking products at temperature, then foams at a higher temperature.
The host agent includes one of polyester, polyethers or urethane oligomer or a variety of, is urethane cures object Base stock.Preferably, host agent of the present invention includes aromatic polyester and aliphatic polyether.Further, the virtue Fragrant adoption ester includes one of polyphenyl dioctyl phthalate ethylene glycol, polyethylene naphthalate, poly- biphenyl dicarboxylic acid glycol ester Or it is a variety of.The aliphatic polyether includes one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly- hexylene glycol or a variety of. The above aromatic polyester and aliphatic polyether all contain two or more C-terminals.
The curing agent is used for the crosslinking of the host agent, and be isocyanate ester compound, can specifically enumerate: toluene two is different Cyanate, methyl diphenylene diisocyanate, naphthalene isocyanates, paraphenylene diisocyanate, hexamethylene diisocyanate, different fluorine One of derivative of that ketone diisocyanate or above-mentioned substance is a variety of.
The foaming agent is used to form porous structure, preferably organic chemistry foaming agent, i.e., is generated gas by thermal decomposition Chemical substance, specifically, can enumerate 2,2'- azodiisobutyronitrile, diisopropyl azodiformate, Barium azodicarboxylate, Diethyl azodiformate, azo amido benzene, nitroso compound class, N, N'- dimethyl-N, N'- dinitroso terephthaldehyde Amide, benzene sulfonyl hydrazide, unifor, 4,4 '-bis oxide benzene sulfonyl hydrazides, 3,3 '-disulfonyl hydrazide diphenyl sulphone (DPS)s, 1,3- benzene, two sulphur Hydrazides, p-toluene sulfonylsemicarbazide, 4,4 '-oxos bis- (benzenesulfonamido- ureas), trihydrazinotriazine, 5- phenyltetrazole etc..Foaming The type and content of agent can be selected according to required pore structure and fabrication process condition.
It include also the process that raw material is prepared into certain shapes, for example pour after raw material mixing in the preparation method It builds, film.
Room temperature or the room temperature or more of being solidificated in carries out, such as 23 DEG C~200 DEG C.But solidification temperature is lower than blowing temperature, So that host agent and curing agent form cross-linking products, and include carbon fiber powder fiber and foaming agent.
The foaming carries out more than solidification temperature, such as 23 DEG C~200 DEG C.Foaming agent decomposes, to form porous structure.
For adjustment aperture, need reasonably to adjust viscosity, the type of foaming agent, the content, blowing temperature of cross-linking products And the time.By adjusting the crosslinking degree of solidification temperature, time adjustable cross-linking products, to adjust the viscous of cross-linking products Degree.
Further, in the preferably described raw material, carbon fiber powder fiber is mixed with the curing agent of part in advance, i.e., first by carbon Fiber dust fiber first with curing agent it is a part of mix after, then mixed with other raw materials and remaining curing agent.This Sample is conducive to improve carbon fiber powder fiber with the interfacial adhesion power of urethane cures object, improves leading for thermosetting resin cured matter Electrical property and mechanical property.It is preferred that carbon fiber powder fiber is mixed with the 30%~60% of curing agent content in advance.
Further, also contain conductive auxiliary agent in the preferably described raw material, the conductive auxiliary agent is that conductive black, carbon are received One of mitron, graphite are a variety of.
Effect and purposes of the invention: present invention incorporates the excellent electric conductivity of carbon fiber powder fiber and polyurethane are solid Compound excellent flexibility and elasticity further improve the electric conductivity and flexibility of solidfied material, make by controlling porous structure Thermosetting resin cured matter softness, tool electric conductivity are obtained, and can be deformed to a certain extent and keep electric conductivity.The present invention The thermosetting resin cured matter can be applied to the fields such as film heating electrode slice, electric heating sheets, Electric radiant Heating Film.
Specific embodiment
Performance evaluation and its evaluation method of the present invention:
(1) it porosity: is measured according to mercury injection method in standard GB/T 21650.1-2008.
(2) average pore size: sample is cut, and observes section using scanning electron microscope, chooses at least 300 holes, meter The amount of counting average pore size, as average pore size.
(3) it tensile strength: is carried out according to GB/T 1447-2005.Sample is cut into I pattern sample, is with a thickness of 2mm, length 180mm；Tensile speed 10mm/min.
(4) flexibility: by be 10mm with a thickness of 2mm, length 90mm, width sample to be placed on an edge be right angle Square mesa on, the half (45mm) of length direction exposes table top.Calculate lowest part and table top that sample exposes countertop segment The angle (taking obtuse angle) that the line at edge is formed with table top.Angle is smaller (i.e. closer to 90 °), then sample exposes the part of table top Degree of sag is bigger, i.e., sample is more soft.
(5) volume resistivity: (unidirectional when undeformed and when deforming according to the measurement sample of GB/T 15662-1995 The volume resistivity of elongation 50%).
Material used in embodiment and comparative example is as follows:
<host agent>
A1: the aromatic polyester comprising polyphenyl dioctyl phthalate ethylene glycol segment, polyethylene naphthalate segment, by following Method preparation: by ethylene glycol (1 molar part), phthalic acid (0.5 molar part), naphthalenedicarboxylic acid (0.5 molar part) and catalyst Sb2O3(0.004 molar part) is uniformly mixed and is warming up to 225 DEG C of reaction certain times, obtains the viscosity at 25 DEG C and exists The polymer of 10000mPas.
A2: the aliphatic poly ether composition comprising polypropylene glycol segment, polytetramethylene glycol segment is prepared as follows: In At 25 DEG C, polypropylene glycol (1000,0.1 molar part of number-average molecular weight), polytetramethylene glycol (650,0.2 molar part of number-average molecular weight) are mixed It closes uniform.
A3: containing the aromatic polyester comprising polyphenyl dioctyl phthalate ethylene glycol segment, polyethylene naphthalate segment and Aliphatic poly ether composition comprising polypropylene glycol segment, polytetramethylene glycol segment, is prepared as follows: at 105 DEG C, by A1 (100 parts by weight), A2 (100 parts by weight) are uniformly mixed.
Above each raw material is purchased from Sigma-Aldrich company.
<curing agent>
B1: hexamethylene diisocyanate is purchased from Sigma-Aldrich company.
<carbon fiber powder fiber>
C1:MLD-30, Japanese Toray Industries, Inc. are produced, and fibre length is 30 μm.
<foaming agent>
D1: azodiisobutyronitrile is purchased from the happy Industrial Co., Ltd. of Shanghai Jin Jin.
D2: Barium azodicarboxylate is purchased from the happy Industrial Co., Ltd. of Shanghai Jin Jin.
<conductive auxiliary agent>
E1: conductive black, hundred million Bo Rui Chemical Co., Ltd. of Tianjin produce, F500A.
Embodiment 1,2, comparative example 1:
By ingredient shown in table 1 and its proportion, host agent, carbon fiber powder fiber, conductive auxiliary agent (if any) are pinched with one Conjunction machine adds curing agent, foaming agent (if any) mixing 2min after 30 DEG C of mixing 6min.Wherein, host agent and curing agent are total 100 parts by weight, and host agent and the proportion of curing agent the isocyanate group molal quantity that is curing agent and host agent hydroxyl are (according to hydroxyl value meter Calculate) molal quantity be 1:1.Then, mixture is moved into mold, after 60 DEG C of solidification 4h, is warming up to the temperature that foams shown in table 1 Degree, foaming inclosed molds 30min obtain thermosetting resin cured matter.Then properties test is carried out, table 2 is as a result listed in.
Embodiment 3~14
By ingredient shown in table 1 and its proportion, in advance with a kneader by conductive auxiliary agent and a part of curing agent in The conductive auxiliary agent mixture containing curing agent is made in 30 DEG C of mixing 2min；By one host agent, carbon fiber powder fiber kneader After 30 DEG C of mixing 6min, the conductive auxiliary agent mixture containing curing agent, remaining curing agent, foaming agent mixing are added 2min.Wherein, host agent and curing agent add up to 100 parts by weight, and host agent and the proportion of curing agent are the isocyanates for making curing agent The molal quantity (being calculated according to hydroxyl value) of the hydroxyl of the molal quantity and host agent of base is 1:1.Then, mixture is moved into mold, in After 60 DEG C of solidification 4h, it is warming up to blowing temperature shown in table 1 (by shown in table 1), foaming inclosed molds 30min obtains thermosetting resin Solidfied material.Then properties test is carried out, table 2 is as a result listed in.
Table 1
Remarks:
P%: the curing agent mixed with the realization of carbon fiber powder fiber accounts for the percentage of curing agent total weight.
/: expression is not added or is not suitable for.
Table 2
Compared with comparative example, thermosetting resin cured matter of the present invention due to suitable porous structure, so With good electric conductivity and flexibility, and preferable electric conductivity is still kept after deformation.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, adds according to technical solution and inventive concept With equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (9)

1. a kind of thermosetting resin cured matter of the tool electric conductivity of softness, which is characterized in that the thermosetting resin cured matter is pressed Listed as parts by weight contains following components:
100 parts by weight of urethane cures object；
10~30 parts by weight of carbon fiber powder fiber；
The thermosetting resin cured matter has porous structure, and porosity is 10~80%, and average pore size is 1~100 micron.
2. a kind of thermosetting resin cured matter of the tool electric conductivity of softness according to claim 1, which is characterized in that described Urethane cures object contains aromatic polyester segment and aliphatic polyether segment.
3. a kind of thermosetting resin cured matter of the tool electric conductivity of softness according to claim 2, which is characterized in that described Aromatic polyester segment includes that aromatic polyester segment includes polyphenyl dioctyl phthalate ethylene glycol segment, polyethylene naphthalate chain One of section, poly- biphenyl dicarboxylic acid glycol ester are a variety of.
4. a kind of thermosetting resin cured matter of the tool electric conductivity of softness according to claim 2, which is characterized in that described Aliphatic polyether segment includes one of polyethylene glycol segment, polypropylene glycol segment, polytetramethylene glycol segment, poly- hexylene glycol segment Or it is a variety of.
5. a kind of thermosetting resin cured matter of the tool electric conductivity of softness according to claim 1-4, feature It is, also contain conductive auxiliary agent, the conductive auxiliary agent is selected from one of conductive black, carbon nanotube, graphite or a variety of.
6. a kind of thermosetting resin cured matter of the tool electric conductivity of softness according to claim 5, which is characterized in that with poly- Urethane solidfied material is 100 parts by weight meters, and the conductive auxiliary agent is 5~15 parts by weight.
7. a kind of a kind of thermosetting resin cured matter of the tool electric conductivity of softnesses described in any item according to claim 1~6 Preparation method, which is characterized in that contain following steps: host agent, carbon fiber powder fiber, curing agent, foaming agent are mixed into obtain institute Raw material is needed, cross-linking products are formed by curing under certain temperature, then foam at a higher temperature；Wherein, the host agent include polyester, One of polyethers or urethane oligomer are a variety of, and the curing agent is isocyanate ester compound, and the foaming agent is that have Chemical machine foaming agent.
8. a kind of preparation method of the thermosetting resin cured matter of the tool electric conductivity of softness according to claim 7, special Sign is that the carbon fiber powder fiber is mixed with partially cured dose in advance.
9. a kind of preparation method of the thermosetting resin cured matter of the tool electric conductivity of softness according to claim 8, special Sign is, conductive auxiliary agent is also contained in the raw material, and the conductive auxiliary agent is one of conductive black, carbon nanotube, graphite Or it is a variety of.
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Application publication date: 20191129