CN114149615B

CN114149615B - Metal acrylate composition, method for producing the same, and resin composition comprising the same

Info

Publication number: CN114149615B
Application number: CN202010919407.XA
Authority: CN
Inventors: 邹秋鹏; 邱冠荣; 陈震玮; 黄亭棣
Original assignee: Sunko Ink Co ltd
Current assignee: Sunko Ink Co ltd
Priority date: 2020-09-04
Filing date: 2020-09-04
Publication date: 2024-02-02
Anticipated expiration: 2040-09-04
Also published as: CN114149615A

Abstract

The invention discloses a high-dispersivity acrylic acid metal salt composition, a preparation method thereof and a resin composition containing the same. In particular, the present invention aims to provide a highly dispersible metal acrylate composition comprising a metal salt of the formula (I) (wherein M ²⁺ And R1 is defined as in the specification), and contains graphene, crystalline flake graphite or a combination thereof with a specific content as a heat conducting powder, thus having better stability and dispersibility, and having the advantages of being not easy to be adhered to a metal surface and easy to be mixed in resin. In addition, the polymer can be used as a crosslinking auxiliary agent in a resin composition to improve the mechanical strength of a finished product, and can ensure that the foamed finished product has good cell uniformity, so that the polymer can be widely applied to interior and exterior decoration materials, household articles, automobile interior decoration materials, door and window and glass frame buffer materials, packaging materials, sports protection pad materials, shoe materials and the like.

Description

Metal acrylate composition, method for producing the same, and resin composition comprising the same

Technical Field

The present invention relates to a metal salt applied to a resin, and more particularly, to a metal acrylate composition having high dispersibility, a method for manufacturing the same, and a resin composition comprising the same.

Background

The metal acrylate is a conventional metal type crosslinking auxiliary agent, can be used as a compounding agent in vulcanization of a rubber composition in combination with a bridging agent, can be used as a modifier in synthesis of a resin, has the effects of improving hardness and compression elasticity of a material, increasing affinity between the material and a metal, improving compatibility between the materials, and improving mechanical strength, stretchability, heat resistance, wear resistance, solvent resistance, tear strength and metal adhesiveness of a plasticized material, and is thus widely used for addition to various plasticized molded products such as golf balls, rollers, sealing strips, cables, belts, building materials and the like.

The structure of the acrylic acid metal salt is shown as the following formula:

wherein M is ²⁺ Is a divalent metal ion, R is a hydrogen group (-H) or a saturated alkyl group.

Common metal acrylates such as zinc acrylate (ZDA), calcium acrylate (calcium diacrylate), magnesium acrylate (magnesium diacrylate). Related products are commercially available such as dyenzyme 633, dyenzyme 634, dyenzyme 705, and dyenzyme 706 from french g Lei Weili (CRAY VALLEY); K-CURE 339, K-CURE 439, K-CURE 633 and K-CURE 634 from Taiwan Sansha Co (SUNKO INK); ZN-DA 90 and ZN-DA 100 from Japanese catalyst Co. The production method is disclosed in patent contents such as taiwan patent publication No. 530062, japanese patent publication No. 58-14416, japanese patent publication No. 4-10463, japanese patent publication No. 4041175, japanese patent publication No. 4286018, japanese patent publication No. 4398157, U.S. patent publication No. 5789616, U.S. patent publication No. 6278010, and U.S. patent publication No. 7217829.

However, the metal acrylate is easily self-polymerized (self-assembled) at high temperature and easily agglomerated (aggregated) with moisture, and in addition, when the metal acrylate is put or stacked for a long time or is pressed heavily, the problem of agglomeration due to compaction is easily caused, and particularly, the problem of the metal acrylate with smaller particle size is more remarkable.

Generally, the metal acrylate is not easy to mix and disperse in rubber after agglomeration, and during mixing, the agglomerated metal acrylate is easy to self-agglomerate and generate viscosity due to friction heat, so that more metal acrylate is adhered; in addition, the metal acrylate is easy to adhere to the metal surface of the equipment, namely, precipitation (plate-out) occurs, and the metal acrylate is difficult to clean, and once the metal acrylate peels off, white spots or flaws are generated on the surface of the rubber product, so that the quality and the appearance are affected.

The problem that the dispersion of the acrylic acid metal salt is difficult can further influence the preparation of the foaming elastomer, and the main reason is that the uneven dispersion of the acrylic acid metal salt can cause uneven bridging density, so that the prepared foaming elastomer has the phenomena of inconsistent cell size, uneven bubble wall thickness, wind packing, bubble breaking and the like, and meanwhile, the problems of poor appearance, insufficient mechanical properties such as tearing strength and the like can be caused.

Regarding the above problems, for example, U.S. patent publication No. 6720364 and taiwan patent publication No. 574296 disclose that a polyolefin foam composition containing zinc diacrylate or zinc dimethacrylate is produced by a secondary press process, which can avoid foam breaking on the surface of a foam molded article to meet physical properties, however, the secondary press process is time consuming, labor consuming and increases production cost.

According to the disclosure of taiwan patent publication No. 648097 and U.S. patent publication No. 10550259B2, it is mentioned that the storage stability of the metal acrylate salt can be improved by using polytetrafluoroethylene wax or polytetrafluoroethylene-modified polyethylene wax as a dispersant. In addition, according to taiwan patent publication No. 647262B, the application of the metal acrylate in a polyolefin elastomer composition provides a foam molding with high reverse elasticity and low compression set without secondary pressing, however, the above patent document does not mention how to avoid the problem of precipitation of the metal acrylate on the sticky metal surface during the conveying process, nor discuss the influence of the metal acrylate on the uniformity of cell dispersion of the foam molding.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a highly dispersible metal acrylate composition which is less likely to adhere to a metal surface during transportation.

Another object of the present invention is to provide a highly dispersible metal acrylate composition which can be used as a crosslinking auxiliary agent in a resin composition to improve the mechanical strength of the final product and to provide the final product with good uniformity of cell dispersion after foaming.

To achieve the foregoing object, the present invention provides a metal acrylate composition comprising:

a metal acrylate, which is shown in formula (I);

in formula (I), M ²⁺ Is zinc ion, magnesium ion or calcium ion, R1 is hydrogen radical or saturated alkyl with 1 to 6 carbon atoms; and

the heat conducting powder is graphene, crystalline flake graphite or a combination thereof, and the content of the heat conducting powder is 0.3 to 25 weight percent based on the total weight of the acrylic acid metal salt composition.

The acrylic acid metal salt composition can improve the stability and the dispersibility of the acrylic acid metal salt composition by containing the acrylic acid metal salt and the specific content of graphene, crystalline flake graphite or the combination thereof, is beneficial to long-time storage or transportation without caking, has the advantages of being not easy to adhere to the metal surface and easy to blend in resin in the transportation process, and can ensure that a finished product has better mechanical strength and foam cell dispersion uniformity after foaming by further applying the acrylic acid metal salt composition to the resin composition.

According to the present invention, the aforementioned metal acrylate composition has a WI value of hue of 20 or more and 70 or less.

Preferably, the content of the heat conductive powder is 0.3 to 8 weight percent based on the total weight of the metal acrylate composition; further, the WI value of the hue of the metal acrylate composition is 30 or more and 70 or less.

More preferably, the content of the heat conductive powder is 0.3 to 2 weight percent based on the total weight of the metal acrylate composition. The content of the heat conducting powder is controlled in the specific range and is applied to the resin composition, and the finished product obtained after foaming can further have the effects of whitening, removing yellow light and fog, and can provide very good appearance and texture; further, the WI value of the hue of the metal acrylate composition is 45 or more and 70 or less.

Preferably, the graphene comprises reduced graphene oxide (reduced graphene oxide, rGO) having a carbon content of 40% or more and a number of layers of 3 to 30; the flake graphite (flat graphite) includes flake graphite having a carbon content of 95% or more and a particle diameter D90 of 5 to 30 μm. More preferably, the graphene includes a thin layer reduced graphene oxide having a carbon content of 60% or more and a number of layers of 3 to 10, an ash value of 0.1 to 2.5 weight percent, and a multi-layer reduced graphene oxide having a carbon content of 60% or more and a number of layers of 10 to 20, an ash value of 0.1 to 2.5 weight percent; the flake graphite comprises flake graphite with carbon content of above 98%, particle diameter D90 of 10-25 microns and ash value of 0.1-1 wt%.

The metal acrylate composition of the present invention may optionally contain additives such as antioxidants, polymerization inhibitors, heat-resistant agents, lubricants, surfactants, or combinations thereof, but is not limited thereto.

The invention also provides a preparation method of the acrylic acid metal salt composition, which comprises the following steps: step (a): reacting acrylic acid, a divalent metal oxide and a heat conducting powder in a nonpolar solvent at a temperature of 30 ℃ to 100 ℃ to obtain a first mixture; step (b): removing the solvent from the first mixture to obtain the metal acrylate composition; the heat conducting powder is graphene, crystalline flake graphite or a combination thereof, and the content of the heat conducting powder is 0.3 to 25 weight percent based on the total weight of the acrylic acid metal salt composition.

Preferably, the step (a) further comprises the steps of: step (a 1): mixing the acrylic acid and the heat conducting powder to obtain a second mixture; step (a 2): reacting the second mixture and the divalent metal oxide in the nonpolar solvent at a temperature of 30 ℃ to 100 ℃ to obtain the first mixture.

Preferably, the molar ratio of the acrylic acid to the divalent metal oxide is 1.4:1 to 2.1:1. More preferably, the molar ratio of the acrylic acid to the divalent metal oxide is from 1.85:1 to 2.05:1.

In the foregoing production method, acrylic acid which is applicable is, for example: 2-propenoic acid (2-propenoic acid), 2-methacrylic acid (2-methylpropenoic acid), 2-ethacrylic acid (2-ethylpropenoic acid), 2-propylacrylic acid (2-propylpropenoic acid), 2-butylacrylic acid (2-butylpropenoic acid), 2-pentylacrylic acid (2-pentylpropenoic acid), 2-hexylacrylic acid (2-hexylpropenoic acid), but are not limited thereto.

In the foregoing process, suitable divalent metal oxides are, for example: zinc oxide, magnesium oxide, calcium oxide, zinc hydroxide, magnesium hydroxide, or calcium hydroxide, but is not limited thereto.

In the above method, the graphene comprises reduced graphene oxide having a carbon content of 40% or more and a number of layers of 3 to 30; the crystalline flake graphite comprises crystalline flake graphite with carbon content of more than 95% and grain diameter D90 of 5-30 microns. Preferably, the graphene comprises a thin layer reduced graphene oxide having a carbon content of 60% or more and a number of layers of 3 to 10, an ash value of 0.1 to 2.5 weight percent, and a multi-layer reduced graphene oxide having a carbon content of 60% or more and a number of layers of 10 to 20, an ash value of 0.1 to 2.5 weight percent; the flake graphite comprises flake graphite with carbon content of above 98%, particle diameter D90 of 10-25 microns and ash value of 0.1-1 wt%.

In the above-mentioned preparation method, the nonpolar solvent refers to hydrocarbon-based solvent with boiling point between 50 ℃ and 150 ℃ under normal pressure; the nonpolar solvents applicable to the present process may be, but are not limited to: benzene, toluene, xylene, cyclohexane, hexane, heptane or octane.

An additive may be optionally added to the above process, and suitable additives include, but are not limited to, antioxidants, inhibitors, heat stabilizers, lubricants, surfactants, or combinations thereof.

According to the invention, the aforementioned additives are contained in an amount of 0.02 to 10% by weight, based on the total weight of the metal acrylate composition.

According to the present invention, the addition of the aforementioned antioxidants can inhibit or prevent oxidative damage during subsequent elastomer production, can inhibit or prevent reactions initiated by oxygen radicals, for example: quinoline antioxidants, amine antioxidants, phenol antioxidants, sulfur antioxidants, and the like, and specific illustrative examples include: the reaction product of N-phenylaniline with 2, 4-trimethylpentene (product of N-phenylaniline reacted with 2, 4-trimethylpentene, CAS No. 68411-46-1), 2, 6-di-tert-butyl-p-cresol (2, 6-di-tert-butyl-4-methyl-phenol), 2'-methylene-bis (4-methyl-6-tert-butylphenol) (2, 2' -methyl-bis (6-tert-butyl-4-methylphen), 4,6-bis (octylthiomethyl) o-cresol (2-methyl-4, 6-bis (octylsulfanylmethyl) phenol), but is not limited thereto; the addition of polymerization inhibitors can slow down the scorch time, such as hydroquinone monomethyl ether (hydroquinone monomethylether), 2, 6-di-tert-butyl-p- (dimethylaminomethyl) phenol (2, 6-di-tert-butyl-4- (dimethyllaminomethyl) phenol), 2, 6-tetramethylpiperidine oxide (2, 6-tetramethylpiperidine) but not limited thereto, the addition of heat-resistant agents can improve the thermal stability, such as fatty acid metal salts but not limited thereto, the addition of lubricants can reduce the frictional heat during the powder transport process, such as fatty acids, low molecular weight polyethylene but not limited thereto, the addition of surfactants can improve the dispersibility, such as polyoxyethylene alkyl ether (polyoxyethylene alkyl ether), sorbitan fatty acid ester (sorbitan fatty acid ester), polyoxyethylene sorbitan fatty acid ester (polyoxyethylene sorbitan fatty acid ester), silicone oil (silicone oil), silicone oil fatty acid ester, sodium alkylbenzenesulfonate (sodium alkylbenzensulfonate), dioctyl sodium succinate (sodium dioctyl sulfosuccinate), and the like, but is not limited thereto.

The present invention further provides a resin composition comprising an unsaturated aliphatic polyolefin and the aforementioned metal acrylate composition.

Preferably, the metal acrylate composition is used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the unsaturated aliphatic polyolefin. More preferably, the metal acrylate composition is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the unsaturated aliphatic polyolefin.

Preferably, the unsaturated aliphatic polyolefin is selected from the group consisting of ethylene propylene diene monomer (ethylene propylene diene monomer rubber, EPDM), butadiene rubber (polybutadiene rubber, BR), butyl rubber (IIR), natural Rubber (NR), isoprene Rubber (IR), and combinations thereof. More preferably, the unsaturated aliphatic polyolefin is selected from the group consisting of ethylene propylene diene monomer synthetic rubber, butadiene rubber, and combinations thereof.

Preferably, the resin composition may further comprise a copolymer, an organic peroxide, a blowing agent, an auxiliary agent, or a combination thereof.

Preferably, the applicable copolymers comprise an ethylene copolymer (ethylene copolymer), a polyolefin block copolymer (olefin block copolymer), or a combination thereof.

Preferably, the ethylene copolymer is selected from the group consisting of ethylene/vinyl acetate copolymer (ethylene/vinyl acetate copolymer), ethylene/octene copolymer (ethylene/octene copolymer), polyethylene (PE), ethylene/alpha-olefin copolymer (ethylene/alpha-olefin copolymer), ethylene/alpha-olefin non-conjugated diene copolymer (ethylene/alpha-olefin non-conjugated diene copolymer), ethylene/acrylic acid copolymer (ethylene/acrylic copolymer), ethylene/methacrylic acid copolymer (ethylene/methyl acrylic copolymer), ethylene/methyl acrylate copolymer (ethylene/methyl acrylate copolymer), ethylene/methyl methacrylate copolymer (ethylene/methyl methacrylate copolymer), ethylene/ethyl acrylate copolymer (ethylene/ethyl acrylate copolymer), ethylene/ethyl methacrylate copolymer (ethylene/ethyl methacrylate copolymer), ethylene/butyl acrylate copolymer (ethylene/butyl acrylate copolymer), ethylene/butyl methacrylate copolymer (ethylene/butyl methacrylate copolymer), and combinations thereof. Still more preferably, the copolymer is selected from the group consisting of ethylene/vinyl acetate copolymers, ethylene/octene copolymers, polyolefin block copolymers, and combinations thereof.

In the resin composition, the weight ratio of the copolymer to the unsaturated aliphatic polyolefin is 1:3 to 3:1.

Preferably, suitable organic peroxides include: alkyl hydroperoxides (alkyl hydroperoxide), dialkyl hydroperoxides (dialkyl hydroperoxide), aromatic hydroperoxides (aromatic hydroperoxide), peroxyacid esters (peroxometers), diperoxide ketals (diperoxyketals), diacyl peroxides (diacyl peroxides) or peroxydicarbonates (peroxocarbonates), but are not limited thereto.

More specifically, the alkyl hydroperoxide may be, but is not limited to: tert-butyl hydroperoxide (tert-butyl-hydroxy-oxy), tert-amyl hydroperoxide (tert-amyl-hydroxy-oxy) or 2,5-dimethyl-2, 5-bis (hydrogen peroxide) hexane (2, 5-dimethyl-hexane-2, 5-dihydroxy-oxy); the dialkyl hydroperoxide may be, but is not limited to: di-tert-butyl hydroperoxide (di-tert-butyl-hydroxy oxide), di-tert-amyl hydroperoxide (di-tert-amyl-hydroxy oxide), 2,5-dimethyl-2, 5-bis (tert-butyl peroxy) -2,5-dimethylhexane (2, 5-dimethyl-2,5-di (tert-butyl peroxy) -hexyne-3) or 2,5-dimethyl-2, 5-bis (tert-butyl peroxy) -hexyne; the aromatic hydroperoxide may be, but is not limited to: dicumyl peroxide (dicumyl peroxide), benzoyl peroxide (benzoyl peroxide), cumene hydroperoxide (cumene hydroperoxide), dicumyl peroxide (diisopropylbenzene hydroperoxide), tert-butyl peroxybenzoate (tert-butyl peroxybenzoate), di (tert-butylperoxyisopropyl) benzene (di-butyl peroxyisopropyl) benzene, bis (4-methylbenzoyl) peroxide (bis (4-methyl benzoyl) peroxide); the peroxyacid esters may be, but are not limited to: tert-butyl peroxybenzoate (tert-butyl peroxybenzoate), tert-amyl peroxybenzoate (tert-amyl peroxybenzoate), tert-butyl peroxyacetate (tert-butyl peroxyacetate), tert-butyl peroxymaleate (tert-butyl monoperoxymaleate), tert-butyl peroxypivalate (tert-butyl peoxypivalate), tert-butyl peroxyneodecanoate (tert-butyl peroxyneodecanoate), tert-amyl peroxyneodecanoate (tert-amyl peroxyneodecanoate), tert-butyl peroxy-2-ethylhexanoate (tert-butyl-2-ethyl-carboxylate), tert-butyl peroxyisobutyrate (tert-butyl peroxyisobutyrate), tert-butyl peroxyneoheptanoate (tert-butyl peroxyneoheptanoate), tert-butyl peroxy-3, 5-trimethylhexanoate (tert-butyl-3, 5-trimethylhexanoate), tert-butyl peroxy-2-ethylcarbonate (tert-butyl-2-ethylhexyl carbonate), tert-ethylhexyl peroxy2-ethylcarbonate (tert-2-methyl-2-diethyl-2-hexane) or 2-dimethyl-2-diethyl-2-hexane (tert-5, 5-dimethyl-2-dimethyl-2-hexane); the diperoxide ketal can be, but is not limited to: 3,6,9-triethyl-3,6,9-trimethyl-1,4, 7-triperoxonane (3, 6,9-trimethyl-1,4, 7-triperoxonane), 1-bis (tert-butyl peroxy) -3, 5-trimethylcyclohexane (1, 1-bis) -3, 5-trimethylcyclohexane), 1-bis (tert-butyl peroxy) cyclohexane (1, 1-bis) or 2, 2-bis (tert-butyl peroxy) butane (2, 2-bis (tert-butyl peroxy) butane); the diacyl peroxide may be, but is not limited to: benzoyl peroxide (bis- (3, 5-trimethylhexanoyl) peroxide (bis (3, 5-trimethyl1-oxohexyl) peroxide) or dilauryl peroxide (dilauroyl peroxide); the peroxydicarbonate may be, but is not limited to: bis (2-ethylhexyl) peroxydicarbonate, bis (2-tert-butylcyclohexyl) peroxydicarbonate, bis (4-tert-butyl-cycloxyl) peroxydicarbonate, bitetradec (dimyrityl peroxyldicarbonate) peroxydicarbonate or bitetradec (dicetyl peroxyducarbonate) peroxydicarbonate.

Preferably, suitable blowing agents include: azo compounds, nitroso compounds or sulfonyl hydrazides, wherein the azo compounds can be azodicarbonamide, azodiisobutyronitrile, diisopropyl azodicarbonate, diethyl azodicarbonate, diazoaminobenzene or barium azodicarbonate; the nitroso compound may be N, N ' -dinitroso pentamethylene tetramine or N, N ' -dimethyl-N, N ' -dinitroso terephthalamide; the sulfonyl hydrazide compound may be 4,4' -disulfonyl hydrazide diphenyl ether, p-benzenesulfonyl hydrazide, 3' -disulfonyl hydrazide diphenyl sulfone, 4' -diphenyldisulfonyl hydrazide, 1, 3-benzenesulfonyl hydrazide, 1, 4-benzenesulfonyl hydrazide, but is not limited thereto.

Suitable adjuvants according to the present invention include fatty acids having 12 to 20 carbon atoms, fatty acid metal salts (e.g., zinc stearate, calcium stearate, barium stearate, etc.), polyethylene wax, zinc oxide, urea, talc, calcium carbonate, titanium dioxide, kaolin, carbon black, pigments, stabilizers, auxiliary crosslinking aids containing vinyl groups (e.g., triallyl cyanurate, triallyl isocyanate, divinylbenzene, triallyl phosphate), or combinations thereof, but are not limited thereto.

The invention also provides a polyolefin elastomer prepared from the resin composition. Specifically, the polyolefin elastomer can be produced by a conventional molding process and production method by a heat vulcanization reaction, for example, a process such as hot press molding, injection molding or extrusion molding, but is not limited thereto.

Preferably, the polyolefin elastomer has a maximum tensile strength of greater than or equal to 110kg/cm ² And less than or equal to 160kg/cm ² . More preferably, the polyolefin elastomer has a maximum tensile strength of greater than or equal to 115kg/cm ² And less than or equal to 140kg/cm ² 。

Preferably, the polyolefin elastomer has a tear strength greater than or equal to 25kg/cm and less than or equal to 50kg/cm. More preferably, the polyolefin elastomer has a tear strength greater than or equal to 30kg/cm and less than or equal to 45kg/cm.

Preferably, the polyolefin elastomer has a compression set of greater than or equal to 10% and less than or equal to 30%.

The invention also provides a foaming elastomer which is prepared from the resin composition. Specifically, the foamed elastomer can be produced by a conventional foaming process, for example, a process such as compression foaming, in-mold foaming or injection foaming, but is not limited thereto.

Preferably, the foamed elastomer has a maximum tensile strength of greater than or equal to 10kg/cm ² And less than or equal to 25kg/cm ² . More preferably, the maximum tensile strength of the foamed elastomer is greater than or equal to 17kg/cm ² And less than or equal to 25kg/cm ² 。

Preferably, the foamed elastomer has a tear strength greater than or equal to 5kg/cm and less than or equal to 15kg/cm. More preferably, the foamed elastomer has a tear strength greater than or equal to 9.7kg/cm and less than or equal to 15kg/cm.

Preferably, the foamed elastomer has a compression set of greater than or equal to 10% and less than or equal to 40%. More preferably, the foamed elastomer has a compression set of greater than or equal to 10% and less than or equal to 35%.

Preferably, the foamed elastomer has a hue WI value of 20 or more and 70 or less, a YI value of-2 or more and 16 or less, and a L value of 45 or more and 85 or less. More preferably, the foamed elastomer has a hue WI value of greater than or equal to 40 and less than or equal to 70, a YI value of greater than or equal to 1 and less than or equal to 11, and a L value of greater than or equal to 70 and less than or equal to 85.

According to the present invention, the foamed elastomer has good uniformity of cell dispersion and mechanical strength, and thus has a wide range of applications, such as building materials, automotive materials, cushioning materials, vibration damping materials, packaging materials, sports pad materials or shoe materials, and the like.

In the specification, a range expressed by "small value to large value" means that the range is greater than or equal to the small value to less than or equal to the large value unless otherwise specified. For example, "0.3 to 25 weight percent" means that it ranges from "greater than or equal to 0.3 weight percent and less than or equal to 25 weight percent".

Drawings

Fig. 1A is a field emission scanning electron micrograph of example 2.

Fig. 1B is a field emission scanning electron micrograph of comparative example 1.

Fig. 2A to 2C are field emission scanning electron micrographs of the foamed elastomer of example 12A at different positions up, middle and down.

Fig. 2D to 2F are field emission scanning electron micrographs of the foamed elastomer of comparative example 3A at different positions up, middle and down.

Detailed Description

Hereinafter, the metal acrylate composition and the resin composition containing the same are described in the embodiments of the present invention by way of examples; those skilled in the art will readily appreciate that many modifications and variations are possible in the exemplary embodiments of the invention without materially departing from the novel teachings and advantages of this invention.

Acrylic acid metal salt composition

The present specification shows the characteristics of the metal acrylate composition of each example in terms of physicochemical properties such as zinc acrylate effective content, heat conductive powder content, ash value (ash), hue, and particle diameter. The physicochemical properties were obtained by the methods described below.

1. Zinc acrylate effective content: the double bond content was analyzed by redox titration to calculate the weight percent (unit:%) of the effective [ zinc acrylate ] in the sample.

2. Ash content: putting 1 gram of sample (initial weight W0) of the fine scale into a high-temperature furnace, heating to 600+/-25 ℃ for 3 hours, taking out to observe the color of powder, putting into the high-temperature furnace again, heating to 800+/-25 ℃ and then holding the temperature for 2 hours, confirming that the carbon consumption is complete, taking out when the residue is gray, putting into a drying box, cooling to room temperature and weighing (residual weight W1); ash values were calculated by the following formula: [ (W0-W1)/W0 ]. Times.100% (unit:%).

3. Content of heat conductive powder: the content of the heat conducting powder is the content of graphene, crystalline flake graphite or a combination thereof in the acrylic acid metal salt composition, namely the weight of the used graphene, crystalline flake graphite or a combination thereof is divided by the total weight of the actually obtained acrylic acid metal salt (unit:%).

4. Hue: hunterLab is selectedThe EZ color difference meter is used for measuring whiteness and yellowness of samples, and the average value of each sample is obtained by three times of testing, so that the average whiteness (WI value) and the average yellowness (YI value) are obtained.

5. Particle size: beckman is selectedLS 13 320/ISO 13320-1 model laser particle diameter instrument, which adopts a micro-module for analysis. Adding ethanol into a balance sample (heat conducting powder sample size is 2 mg; acrylic acid metal salt composition sample size is 0.15 g) to disperse to 100 ml, oscillating with ultrasonic wave for 1 min, injecting into a container of a micro-module until the shielding rate reaches 10%, analyzing, recording 90% particle size (D90) and average particle size (D50), and leveling three times for each sample testMean and counted in Volume (micrometers).

Example 1

As the heat conductive powder, 5.83 g of graphene (multi-layer reduced graphene oxide having a carbon content of 99% or more, an ash value of 0.5 wt% or less, and a number of layers of 10 to 20, purchased from taiwan security company) was selected, and was uniformly mixed with 1048 g (14.55 mol) of acrylic acid (hydroquinone monomethyl ether 200±20ppm, purchased from taiwan plastic industries, co.) to obtain a second mixture.

A6 liter stainless steel reaction vessel was selected and charged with 2000 ml of toluene, 586.4 g (7.24 moles) of zinc oxide, 102.3 g (0.36 moles) of stearic acid and 4.8 g of a nonionic surfactant (Sinopol 1807), heated to 50.+ -. 5 ℃ after stirring uniformly, and then the second mixture was added to react at a controlled temperature of 50 ℃ to 80 ℃ for 2 hours to obtain a first mixture.

The first mixture was distilled under reduced pressure to remove about 129 ml of water produced by the reaction while recovering toluene, followed by continuous drying until the water content of the first mixture was less than 2000ppm, cooling to room temperature to obtain a crude product, and subjecting the crude product to high-speed jet mill (model RT-25) to deagglomeration to obtain 1587 g of a powdery product, namely the zinc acrylate salt composition of example 1. The properties of the zinc acrylate salt composition of example 1 were analyzed in the manner previously described to give an effective zinc acrylate content: 92.3%; ash value: 36.7%; particle size: d50 is 6.42 microns and D90 is 21.0 microns; hue: WI is 65.5 and YI is-1.8; content of heat conductive powder: 0.367%.

Example 2

This example generally employs the process described in example 1 above to prepare a zinc acrylate salt composition, with the exception that: in example 2, 12.19 g of graphene (multi-layer reduced graphene oxide with carbon content of 99% or more, ash content of 0.5 wt% or less and number of layers of 10 to 20 obtained from taiwan's safety company) was selected as the heat conductive powder, and 1577 g of powdery product was finally obtained, namely the zinc acrylate composition of example 2. Analysis of the characteristics of the zinc acrylate salt composition of example 2 in the manner previously described gave zinc acrylate effective content: 91.2%; ash value: 36.8%; particle size: d50 is 5.66 microns and D90 is 17.9 microns; hue: WI is 55.0 and YI is-2.0; content of heat conductive powder: 0.773%.

Example 3

This example generally employs the process described in example 1 above to prepare a zinc acrylate salt composition, with the exception that: in example 3, 24.57 g of graphene (multi-layer reduced graphene oxide with carbon content of 99% or more, ash content of 0.5 wt% or less and number of layers of 10 to 20 obtained from taiwan's Anqiang company) was selected as the heat conductive powder, and 1600 g of a powdery product was finally obtained, namely the zinc acrylate composition of example 3. Analysis of the characteristics of the zinc acrylate salt composition of example 3 in the manner previously described gave zinc acrylate effective content: 91.8%; ash value: 36.8%; particle size: d50 is 7.41 microns and D90 is 20.8 microns; hue: WI is 50.8 and YI is-2.5; content of heat conductive powder: 1.54%.

Example 4

This example generally employs the process described in example 1 above to prepare a zinc acrylate salt composition, with the exception that: in example 4, 32.92 g of graphene (multilayer reduced graphene oxide with carbon content of 99% or more, ash content of 0.5 wt% or less and number of layers of 10 to 20, purchased from taiwan's Angu company) was selected as the heat conductive powder, and 1605 g of the powdery product was finally obtained, namely the zinc acrylate composition of example 4. Analysis of the characteristics of the zinc acrylate salt composition of example 4 in the manner previously described gave zinc acrylate effective content: 90.4%; ash value: 36.2%; particle size: d50 is 7.47 microns and D90 is 22.6 microns; hue: WI is 49.6 and YI is-3.0; content of heat conductive powder: 2.05%.

Example 5

This example generally employs the process described in example 1 above to prepare a zinc acrylate salt composition, with the exception that: in example 5, 139.3 g of graphene (multilayer reduced graphene oxide with carbon content of 99% or more, ash content of 0.5 wt% or less and number of layers of 10 to 20 obtained from taiwan kangfu) was selected as the heat conductive powder, and 1752 g of a powdery product was finally obtained, namely the zinc acrylate composition of example 5. Analysis of the characteristics of the zinc acrylate salt composition of example 5 in the manner previously described gave zinc acrylate effective content: 86.9%; ash value: 36.8%; particle size: d50 is 8.43 microns and D90 is 20.7 microns; hue: WI is 33.0 and YI is-2.9; content of heat conductive powder: 7.95%.

Example 6

5.83 g of graphene (thin-layer reduced graphene oxide with carbon content of 60-80%, ash content of less than or equal to 2.5 weight percent and layer number of 3-10 layers, which is purchased from Taiwan Angu, china) is selected as heat conducting powder, and is placed into a 6-liter stainless steel reaction tank, 2000 ml of toluene, 1048 g (14.55 mol) of acrylic acid, 586.4 g (7.24 mol) of zinc oxide, 102.3 g (0.36 mol) of stearic acid and 4.8 g of silicone oil are added into the stainless steel reaction tank, and the mixture is heated to 50+/-5 ℃ for reaction after being stirred uniformly, wherein the reaction process is controlled to be at 50-80 ℃ and the reaction temperature is continuously stirred for 2 hours, and then the first mixture is obtained.

The first mixture was distilled under reduced pressure to remove about 129 ml of water produced by the reaction while recovering toluene, followed by continuous drying until the water content of the first mixture was less than 2000ppm, cooling to room temperature to obtain a crude product, and subjecting the crude product to high-speed jet mill (model RT-25) to deagglomeration to obtain 1587 g of a powdery product, namely the zinc acrylate salt composition of example 6. Analysis of the characteristics of the zinc acrylate salt composition of example 6 in the manner previously described gave zinc acrylate effective content: 92.3%; ash value: 36.7%; particle size: d50 is 7.85 microns and D90 is 20.3 microns; hue: WI is 59.4 and YI is-1.3; content of heat conductive powder: 0.367%.

Example 7

This example generally employs the process described in the preceding example 6 to prepare a zinc acrylate salt composition, with the exception that: in example 7, 12.19 g of graphene (multi-layer reduced graphene oxide with carbon content of 99% or more, ash content of 0.5 wt% or less and number of layers of 10 to 20 obtained from taiwan's safety company) was selected as the heat conductive powder, and 1624 g of a powdery product was finally obtained, namely the zinc acrylate composition of example 7. Analysis of the characteristics of the zinc acrylate salt composition of example 7 in the manner previously described gave zinc acrylate effective content: 91.65%; ash value: 37.2%; particle size: d50 is 10.1 microns and D90 is 22.7 microns; hue: WI is 64.46 and YI is-2.37; content of heat conductive powder: 0.751%.

Example 8

This example generally employs the process described in the preceding example 6 to prepare a zinc acrylate salt composition, with the exception that: in example 8, 12.19 g of crystalline flake graphite (crystalline flake graphite obtained from Qingdao and having carbon content of 99.48%, ash content of 0.52% and particle size D90 of 12.27 μm) was selected as the heat conductive powder, and 1626 g of a powdery product, namely, the zinc acrylate salt composition of example 8, was finally obtained. Analysis of the characteristics of the zinc acrylate salt composition of example 8 in the manner previously described gave zinc acrylate effective content: 91.39%; ash value: 37.13%; particle size: d50 is 18 microns and D90 is 29.8 microns; hue: WI is 62.12 and YI is-2.29; content of heat conductive powder: 0.750%.

Example 9

This example generally employs the process described in the preceding example 6 to prepare a zinc acrylate salt composition, with the exception that: in example 9, 403.3 g of graphene (multilayer reduced graphene oxide with carbon content of 99% or more, ash content of 0.5 wt% or less and number of layers of 10 to 20 obtained from taiwan kangfu company) was selected as the heat conductive powder, and 1936 g of powdery product was finally obtained, namely the zinc acrylate composition of example 9. Analysis of the characteristics of the zinc acrylate salt composition of example 9 in the manner previously described gave zinc acrylate effective content: 78.9%; ash value: 34.6%; particle size: d50 is 8.64 microns and D90 is 23.9 microns; hue: WI is 25.8 and YI is-2.75; content of heat conductive powder: 20.8%.

Example 10

13.3 g of graphene (multi-layer reduced graphene oxide with carbon content of more than 99 percent, ash content of less than or equal to 0.5 weight percent and layer number of 10 to 20 layers, which is purchased from taiwan Angu company) is selected as heat conduction powder, and is placed into a 6-liter stainless steel reaction tank, 2000 ml of cyclohexane, 1252 g (14.55 mol) of methacrylic acid, 586.4 g (7.24 mol) of zinc oxide and 4.8 g of silicone oil are added into the reaction tank, and the mixture is heated to 50+/-5 ℃ for reaction after being stirred uniformly, wherein the reaction process is controlled to be at 50-80 ℃ and the mixture is continuously stirred for 2 hours.

The first mixture was distilled under reduced pressure to remove about 129 ml of water produced by the reaction while recovering cyclohexane, followed by continuous drying until the water content of the first mixture was less than 2000ppm, cooling to room temperature to obtain a crude product, and subjecting the crude product to high-speed jet mill (model RT-25) to deagglomeration to obtain 1794 g of a powdery product, namely, zinc methacrylate salt composition of example 10. The characteristics of the zinc methacrylate salt composition of example 10 were analyzed in the manner previously described to give an effective zinc methacrylate content: 96.14%; ash value: 31.65%; particle size: d50 is 8.7 microns and D90 is 24.6 microns; hue: WI is 49.28, yi is 4.14; content of heat conductive powder: 0.74%.

Comparative example 1

A6 liter stainless steel reaction vessel was selected, and 2000 ml of toluene, 1048 g (14.55 mol) of acrylic acid, 586.4 g (7.24 mol) of zinc oxide, 102.3 g (0.36 mol) of stearic acid and 4.8 g of silicone oil were added thereto, and after stirring uniformly, the reaction was carried out by heating to 50.+ -. 5 ℃ with the reaction temperature controlled between 50 ℃ and 80 ℃ and stirring was continued for 2 hours to obtain a mixture.

The mixture was distilled under reduced pressure to remove about 129 ml of water produced by the reaction while recovering toluene, followed by continuous drying until the water content of the mixture was less than 2000ppm, cooling to room temperature to obtain a crude product, and subjecting the crude product to deagglomeration in a jet mill (model RT-25) to obtain 1581 g of a powdery product, namely the zinc acrylate composition of comparative example 1. Analysis of the properties of the zinc acrylate salt composition of comparative example 1 in the manner described above gave zinc acrylate effective content: 91.6%; ash value: 36.0%; particle size: d50 is 7.55 microns and D90 is 20.1 microns; hue: WI is 91.6 and YI is-0.27.

Comparative example 2

A6L stainless steel reaction tank is selected, 2000 ml cyclohexane, 1252 g (14.55 mol) methacrylic acid, 586.4 g (7.24 mol) zinc oxide and 4.8 g silicone oil are added into the reaction tank, the reaction tank is heated to 50+/-5 ℃ after being uniformly stirred, the reaction process is controlled to be at 50-80 ℃ and the reaction is carried out after continuously stirring for 2 hours, so that a mixture is obtained.

The mixture was distilled under reduced pressure to remove about 129 ml of water produced by the reaction while recovering cyclohexane, followed by continuous drying until the water content of the mixture was less than 2000ppm, cooling to room temperature to obtain a crude product, and subjecting the crude product to deagglomeration in a jet mill (model RT-25) to obtain 1788.9 g of a powdery product, namely the zinc methacrylate salt composition of comparative example 2. The characteristics of the zinc methacrylate salt composition of comparative example 2 were analyzed in the foregoing manner to give zinc methacrylate effective content: 97.65%; ash value: 32.36%; particle size: d50 is 7.8 microns and D90 is 37.9 microns; hue: WI is 89.85 and YI is 1.95.

The main difference in the preparation of zinc acrylate salt compositions according to examples 1 to 10 and comparative examples 1 to 2 described above is whether graphene or crystalline flake graphite is added as a heat conductive powder during the preparation. The comparison of the differences of the heat conductive powder between the examples and the comparative examples is shown in Table 1.

Table 1: comparison of the heat conductive powders contained in the zinc acrylate salt compositions of examples 1 to 10 and comparative examples 1 to 2.

To confirm the superior stability, dispersibility and anti-sticking property of the metal acrylate composition of the present invention during storage or transportation, the following test example 1 was used to simulate the influence of the metal acrylate composition after being subjected to a heavy pressure during storage or transportation; the morphology of the metal acrylate composition under the micro level was directly observed in test example 2 to evaluate the dispersibility thereof; the process of delivering the metal acrylate composition in the feeder was simulated as in test example 3 to observe the anti-sticking property to the metal equipment after the completion of the delivery. In addition, the thermal conductivity of the metal acrylate composition was shown in test example 4; the dispersibility of the heat conductive powder in the metal acrylate composition was observed by an optical microscope in test example 5.

Test example 1: metal acrylate composition weight test

This test example was conducted with zinc acrylate salt compositions of examples 2, 8 and 9 and comparative example 1. The specific steps are that 3 bags of 100 g of samples in the zinc acrylate salt compositions of different groups are respectively placed in aluminum foil bags with the size of 10 cm multiplied by 10 cm, air in the aluminum foil bags is extruded, then heat sealing is carried out, and then 4 kg of flanges (flanges) are placed on the aluminum foil bags after heat sealing and placed in a baking oven with the temperature of 50 ℃, so that the heavy pressure and temperature conditions possibly suffered by the metal acrylate salt compositions in the process of transportation or storage are simulated. The test time of test example 1 is given in month, and the appearance states of each group are listed in table 2, which are different from one month, two months, and three months of repression.

Table 2: appearance of zinc acrylate salt compositions of examples 2, 8 and 9 and comparative example 1 when pressed for one month, two months and three months.

As is clear from the results of table 2, the group of examples 2, 8 and 9 is superior in stability and dispersibility to the case of storing or transporting the zinc salt composition because the zinc salt composition of acrylic acid contains the heat conductive powder, and the zinc salt composition of example 9 contains the highest amount of the heat conductive powder (20.8 wt%) as compared with the group of comparative example 1 to which the heat conductive powder was not added, and thus the appearance state after three months of heavy pressing does not appear as a powder lump.

Test example 2: morphology observations of acrylic acid metal salt compositions

The morphology of the zinc acrylate salt compositions of example 2 and comparative example 1 was photographed under a magnification of 2000 times using a field-emission scanning electron microscope (field-emission scanning electron microscope, FE-SEM; model JOEL JSM-6700F), and the results are shown in FIGS. 1A and 1B.

As can be seen from comparing fig. 1A and 1B, the composition of zinc acrylate salt of example 2 is well-defined in shape and free of large agglomerates; a larger agglomeration was observed for the zinc acrylate salt composition of comparative example 1. From this, it is understood that the zinc acrylate salt composition of example 2 does have better dispersibility than that of comparative example 1.

Test example 3: evaluation of tackiness of acrylic Metal salt composition to Metal surface

Before the test, the zinc acrylate compositions of example 2 and comparative example 1 were dried in an oven at 50 ℃ for 3 hours and then returned to room temperature, 100 g of the zinc acrylate composition was sampled and placed into a biaxial screw feeder, respectively, to carry out a procedure of transporting powder, after the transporting procedure was completed, the surface of a metal member of the feeder was observed for the sticking and residue of the powder, and then the powder remaining on the surface of the metal member was collected and weighed to evaluate the sticking to the metal surface.

The powder weight of the zinc acrylate salt composition of example 2 remaining on the surface of the metal member was 2.92 g; the weight of the powder of the zinc acrylate salt composition of comparative example 1 remaining on the surface of the metal member was 10.23 g. From the measured residual weight of powder, the zinc acrylate salt composition of example 2 hardly adhered to the surface of the metal member, showing a relatively small amount of powder residual; the zinc acrylate salt composition of comparative example 1 was found to have a remarkably high tackiness to the surface of the metal member, resulting in a large amount of powder remaining on the metal surface, that is, the zinc acrylate salt composition of example 2 had a low tackiness to the metal surface as compared with comparative example 1, and a large amount of powder did not remain on the metal surface.

Test example 4: thermal conductivity of metal acrylate compositions

In this test example, a multilayer reduced graphene oxide (obtainable from taiwan security corporation, taiwan, and having a carbon content of 99% or more and a number of layers of 10 to 20), a zinc acrylate salt composition of example 5 and comparative example 1 were used as samples, and a Hot Disk thermal conductivity meter (obtainable from TechMark corporation, model TPS 3500) was used to measure the thermal conductivity according to the ISO-DIS22007-2.2 standard. The specific procedure was to take the samples and compact them into ingots, and then to measure the thermal conductivity with a Hot Disk thermal conductivity meter, and the results are shown in Table 3.

Table 3: thermal conductivity of the multilayer reduced graphene oxide, zinc acrylate compositions of example 5 and comparative example 1.

As can be seen from the results of table 3, the gold acrylate composition of example 5 significantly improved the thermal conductivity by about 2.5 times and was close to that of the multi-layered reduced graphene oxide because it contained a certain proportion of the thermal conductive powder (graphene) as compared with the zinc acrylate composition of comparative example 1, which did not contain the thermal conductive powder.

Test example 5: evaluation of dispersibility of thermally conductive powder in acrylic acid metal salt composition

This test example was conducted using three groups of the multilayer reduced graphene oxide (obtained from taiwan security company, taiwan, and having a carbon content of 99% or more and a number of layers of 10 to 20), the zinc acrylate composition of example 2, and the zinc acrylate composition of comparative example 1, with the addition of the aforementioned multilayer reduced graphene oxide, as samples. There are two methods for evaluating dispersibility in this test example: the evaluation method (1) is to take 6 milligrams of the samples, respectively mix the samples with 250 milligrams of silicone oil, observe the samples with an optical microscope after uniformly stirring the samples, select the values with the first five major sheet diameters in the observed black sheet (representing the aggregate of the heat conducting powder) under the condition that the light brightness is the brightest, and record the values after the values are averaged; evaluation method (2) the particle size was analyzed by laser, and after the sample was dispersed in ethanol by ultrasonic vibration for 1 minute, the particle sizes D90 and D50 were recorded. The results of the foregoing evaluation methods (1) and (2) are shown in Table 4.

Table 4: the dispersibility evaluation results of three groups of the multilayered reduced graphene oxide, the zinc acrylate salt composition of example 2, and the zinc acrylate salt composition of comparative example 1, with the addition of the multilayered reduced graphene oxide.

As can be seen from the results of table 4, regarding the results of the evaluation method (1), the black flakes in example 2 had the lowest average flake size, i.e., the aggregate containing the smallest-sized heat conductive powder, which represented that the heat conductive powder in example 2 had good dispersibility, and it can also be seen from the results of the previous five major flakes that example 2 had a lower flake size and the flake sizes between the black flakes were also closer, thereby also showing good dispersibility. In addition, as for the result of the evaluation method (2), example 2 also had the lowest particle diameter D90 and particle diameter D50, and thus it was also confirmed that it had good dispersibility.

Resin composition

The aforementioned metal acrylate composition was further applied to the resin composition and simultaneously compared with a group to which no metal acrylate composition was added to evaluate differences in properties of hardness, specific gravity, maximum tensile strength, elongation at break, tear strength, compression set, reverse-pulling elasticity, and hue. The aforementioned characteristics are obtained by the following method.

1. Hardness: cutting the sample into a round or square test piece having a thickness of at least 6 mm according to the D2240 standard defined by ASTM, and measuring the test piece with a Shore A durometer (manufacturer: TECLOCK; model: GS-709N) on a sample of the polyolefin elastomer with the center of the test piece at least 12 mm from each side; samples of the foamed elastomer were measured using a Shore C durometer (manufacturer: TECLOCK; model: GS-701N TYPE C) at a temperature of 23.+ -. 2 ℃ and the data were read in a hand-held manner and the average of the five data was taken as the measured hardness.

2. Specific gravity: the sample was cut into test pieces of 3X 2.5X 1 cm in size according to the D792 standard defined by ASTM, placed in an environment at a temperature of 23.+ -. 2 ℃ and a humidity of 50.+ -. 10% for at least 40 hours, and weighed at a temperature of 23.+ -. 2 ℃ by an electronic balance (manufacturer: percisa; model: 125A SCS), three sets of weight data were taken, averaged and the specific gravity (unit: g/cm) was calculated ³ )。

3. Maximum tensile strength: according to the D412 standard defined by ASTM, a sample is cut into test pieces by a die C-type cutter, and the test pieces are measured at a tensile speed of 500.+ -. 50 mm per minute using a tensile tester (manufacturer: high-speed rail technology; model: AI-7000S) at a temperature of 23.+ -. 2 ℃ in three groups, and the average of the data of the three groups is taken as the maximum tensile strength (unit: kg/cm) ² )。

4. Elongation at break: the test pieces were cut into test pieces using a die C-type cutter according to the D412 standard defined in ASTM, and then measured using a tensile tester (manufacturer: high-speed rail technology; model: AI-7000S) at a temperature of 23.+ -. 2 ℃ and at a tensile speed of 500.+ -.50 mm per minute, the number of the test pieces was three, and the average value of the three sets of data was taken as elongation at break (unit:%).

5. Tear strength: the sample was cut into test pieces having a thickness of 1 cm by a die C type cutter according to the D624 standard defined by ASTM, and the test pieces were measured at a tensile speed of 500.+ -. 50 mm per minute using a tensile tester (manufacturer: high-speed rail technology; model: AI-7000S) at a temperature of 23.+ -. 2 ℃ in three groups, and the average value of the data of the three groups was taken as the tear strength (unit: kg/cm).

6. Compression set: method B (C) in the D395 standard defined according to ASTM _B ) The sample was cut into round test pieces having a diameter of 29.0.+ -. 0.5 mm, and a permanent compression distortion tester (manufacturer: high-speed rail technology; model: GT-7049) and the test piece are placed in an environment with a temperature of 23+ -2deg.C and a humidity of 50+ -10% for at least 3 hours, followed by The test pieces were placed on a pad in a permanent compression distortion tester and compressed to 50% of the original sample thickness, and continuously compressed at a temperature of 23.+ -. 2 ℃ for 22 hours, the thickness of the test pieces was measured after releasing the pressure for 30 minutes, at least 2 groups of test pieces were measured, the compression set was calculated after calculating the average value thereof, and the calculation formula of the compression set was as follows (unit:%):

C _B ＝[(t _o -t _i )/(t _o -t _n )]×100％；

C _B percent compression set;

t _o test piece initial thickness (original thickness of the specimen);

t _i =test piece final thickness (final thickness of the specimen);

t _n pad thickness (thickness of the space bars used).

7. Reverse poking elasticity: the sample was cut into test pieces having a thickness of 12.5.+ -. 0.5 mm according to the standard D2632-2001 (2008) defined by ASTM, the center of each test piece was set to be at least 14 mm away from each side, then a vertical elastic tester (manufacturer: high-speed iron technology, model: GT-7042-V1) was used at a temperature of 23.+ -. 2 ℃ to let 28 g of impact hammer fall from a release height of 40 cm on the test piece, and then the vertical rebound heights of the impact hammers were visually read by ruler, and 3 groups of test pieces were measured in total, each test piece was measured 6 times, taking the ratio (unit:%) of the vertical rebound heights of the impact hammers at 4 th to 6 th times on average.

8. Hue: hunterLab is selectedThe EZ color difference meter was used to measure whiteness, yellowness and brightness of the foamed elastomer without skin, and each sample was tested three times to obtain average whiteness (WI value), average yellowness (YI value) and average brightness (L value).

Test example 6: auxiliary crosslinkability test of acrylic Metal salt composition

This test example uses zinc acrylate of example 2 and comparative example 1The salt composition was subjected to an auxiliary crosslinkability test. The formulation and preparation of the resin composition samples used in the measurement were as follows, based on 100 weight percent of cis-butadiene rubber (product number BR40 and purchased from Taiwan Qimen Co., ltd.), 29 weight percent of the metal acrylate composition, 18 weight percent of zinc oxide, 1.5 weight percent of dicumyl peroxide, and then the above raw materials were uniformly kneaded by a plastic spectrometer at a process control temperature of 45℃to 65℃until the mixture was uniform, 6 g of which was weighed and subjected to vulcanization curve analysis (control parameter: 170℃C/10 min/swing angle: 0.5 ℃) by a closed type sulfur transformer (manufacturer: model: EKT-2000S) and the lowest torque (M) was recorded _L ) Maximum torque (M) _H ) The scorch time (Ts 2) and the sulfur change time (Tc 90) are listed in Table 5 below.

Table 5: results of analysis of vulcanization curves of the resin compositions added in example 2 and comparative example 1.

As is clear from the results of table 5, even though graphene is contained as the heat conductive powder in the zinc acrylate salt composition of example 2, the progress of vulcanization was not affected, and it was revealed that the zinc acrylate salt composition of example 2 also has good auxiliary crosslinking characteristics.

Examples 11 to 21: resin composition

The raw materials of the "resin composition" of the following examples include a copolymer (A), an unsaturated aliphatic polyolefin (B), an organic peroxide (C), a metal acrylate composition (D), an auxiliary agent (E) and a blowing agent (F). In addition, the resin composition may further include a filler (G).

Wherein the copolymer (A) is selected from ethylene/vinyl acetate copolymer (A1) (available from Taiwan polymerization Co., china; trade name: EVATHENE UE-634); the unsaturated aliphatic polyolefin (B) may be selected from: ethylene propylene diene monomer (B1) (available from DOW; trade name: nordel IP 4570), butadiene rubber (B2) (available from Taiwan Qimei; trade name: BR 40) or a mixture thereof; the organic peroxide (C) is dicumyl peroxide (C1) (available from Juntai chemical company; trade name: ACEOX DCP); the metal acrylate composition (D) may be selected from the metal acrylate compositions of the foregoing examples 1 to 10; the auxiliary agent (E) can be selected from the following components: stearic acid (E1), zinc stearate (E2), zinc oxide (E3) or mixtures thereof; the foaming agent (F) is selected from azodicarbonamide (F1) (available from Junta chemical company; trade name: ACEOX AC 3000); the filler (G) may be calcium carbonate (G1).

Firstly, the copolymer (A), the unsaturated aliphatic polyolefin (B), the acrylic acid metal salt composition (D) and the auxiliary agent (E) are added to a kneader (manufacturer: leaching machine; model: KD-3-20), melt-kneaded at a temperature of 60℃to 100℃and a rotational speed of 40rpm for 5 minutes, and then the organic peroxide (C) and the foaming agent (F) are added, and melt-kneaded at a temperature of 80℃to 100℃and a rotational speed of 40rpm for 5 minutes to form a resin composition.

In the resin compositions of examples 11 to 21, the amounts of the auxiliary (E) stearic acid (E1), zinc stearate (E2) and zinc oxide (E3) were fixed to 0.88 parts by weight, 1.36 parts by weight and 2.24 parts by weight, respectively, in terms of 100 parts by weight (also referred to as 100 phr) of the unsaturated aliphatic polyolefin (B) and the other materials in terms of relative parts by weight. The components of the remaining compositions in the resin compositions of examples 11 to 21 except for the fixed amounts of the auxiliary agents and the amounts are listed in Table 6 below. By controlling the ratio, the influence of the metal acrylate composition (D) on the properties of the resin composition can be examined.

Comparative examples 3 to 6 and comparative example 1: resin composition

Comparative examples 3 to 6 and comparative example 1 resin compositions were prepared substantially by the method as in examples 11 to 21, except that the zinc acrylate salt compositions of the foregoing comparative examples 1 and 2 were selected for the metal acrylate salt composition (D) in the resin compositions of comparative examples 3 to 6; the metal acrylate composition (D) was not added to the resin composition of comparative example 1. The components of the resin compositions of comparative examples 3 to 6 and comparative example 1 and the amounts of the respective components are also shown in Table 6 below.

Table 6: the constituent components and the amounts of the respective components of the resin compositions of examples 11 to 21, comparative examples 3 to 6 and comparative example 1.

/>

Examples 19A to 21A and comparative examples 5A, 6A: polyolefin elastomer

The resin compositions of examples 19 to 21 and comparative examples 5 and 6, which did not contain a foaming agent, were calendered into a film by a twin-roll mixer (manufacturer: xufeng, model: HF-2 RM).

Next, 32 g of the film sample containing no foaming agent was placed in the center of a metal mold having a thickness of 2 mm, a length of 120 mm and a width of 120 mm, and then heated to 165.+ -. 5 ℃ at 100.+ -. 5kg/cm ² The polyolefin elastomers of examples 19A to 21A and comparative examples 5A and 6A were obtained by heating under pressure for 10 minutes.

Examples 11A to 18A, comparative examples 3A, 4A and comparative example 1A: foamed elastomer

The resin compositions containing the blowing agent of examples 11 to 18, comparative examples 3, 4 and comparative example 1 were selected and cut into pellets of about 3 mm in length by a granulator (manufacturer: letaking machine, model: KD-FR-50) or calendered into a film by a twin-roll mixer (manufacturer: xufeng, model: HF-2 RM).

Next, the above-obtained colloidal particles or film was placed in a mold having a thickness of 8 mm, a length of 120 mm and a width of 50 mm, and sampled 42 g at a temperature of 165.+ -. 5 ℃ and 160.+ -. 10kg/cm ² The foamed elastomers of examples 11A to 18A, comparative examples 3A, 4A and comparative example 1A were produced in this order by heating under pressure for 10 to 20 minutes.

The polyolefin elastomers of examples 19A to 21A and comparative examples 5A and 6A and the foamed elastomers of examples 11A to 18A, comparative examples 3A, 4A and comparative example 1A were all tested by the above-described methods to obtain the results of hardness, specific gravity, maximum tensile strength, elongation at break, tear strength, compression set, reverse-pulling elasticity, hue and the like, and are shown in Table 7. In addition, in order to evaluate the effect of the content of the heat conductive powder contained in the metal acrylate composition of the present invention on the characteristics of the resin composition, the content of the heat conductive powder in the resin composition (in Table 7, simply referred to as the content of the heat conductive powder [ resin ]) is also shown in Table 7, which is calculated by multiplying the weight of the metal acrylate composition (D) by the content of the heat conductive powder shown in Table 1, and dividing by the total weight of the resin composition in parts per million (ppm).

Table 7: polyolefin elastomers of examples 19A to 21A and comparative examples 5A, 6A and foamed elastomers of examples 11A to 18A, comparative examples 3A, 4A and comparative example 1A.

/>

First, examples 11A to 17A and comparative example 3A each were a group comprising ethylene propylene diene monomer (B1) as the unsaturated aliphatic polyolefin (B) and a foaming agent was added thereto, and the composition was controlled to be the same except for the metal acrylate composition, so that the difference in the results of the group was presumed to be different in the composition and the amount of the metal acrylate composition to be added. For evaluation of mechanical properties such as maximum tensile strength and tear strength of the foamed elastomer, please refer to test results of maximum tensile strength and tear strength of the foamed elastomers of examples 11A to 16A and comparative example 3A in table 7, which are 16.6kg/cm respectively compared with the maximum tensile strength and tear strength of comparative example 3A ² And 9.58kg/cm, the maximum tensile strength and tear strength of examples 11A to 16A are clearly improved to a considerable extent. As can be seen from the above, the foamed elastomers of examples 11A to 16A contain the heat conductive powder of the present inventionTherefore, the metal acrylate composition has better maximum tensile strength and tearing strength, namely has the effect of improving mechanical strength. Furthermore, referring again to example 17A, which is a group in which calcium carbonate was additionally added as a filler, it was also observed from the experimental results of the maximum tensile strength and tear strength in table 7 that the maximum tensile strength and tear strength of example 17A were still significantly better than those of comparative example 3A.

In example 18A and comparative example 4, the unsaturated aliphatic polyolefin (B) was a cis-butadiene rubber (B2) and the foaming agent was added, and the composition was controlled to be the same except for the metal acrylate composition, so that the difference in the results of the above groups was estimated to be different in the composition and the amount of the metal acrylate composition to be added. As is clear from the test results in Table 7, the maximum tensile strength and the tear strength were 13.4kg/cm, respectively, as compared with comparative example 4A ² And 7.5kg/cm, the maximum tensile strength and tear strength of example 18A being 13.5kg/cm ² And 8.2kg/cm, also showed an improvement in mechanical properties, and the compression set of example 18A was 13.5%, which is superior to that of comparative example 4A (15.1%).

In addition, please refer to the hue test results of examples 11A to 13A and comparative example 3A. In general, when graphene, flake graphite, or a combination thereof is added as a heat conductive powder to a resin composition, it is expected that the Whiteness (WI) thereof will be reduced therewith, however, it is found from the results of WI of examples 11A to 13A and comparative example 3A that when the heat conductive powder is present in a specific content in the resin composition, it is unexpectedly further capable of producing a whitening effect, and further comparing the results of Yellowness (YI) and brightness (L) of examples 11A to 13A and comparative example 3A, it shows that the heat conductive powder having a specific content in the resin composition can also have an effect of reducing yellowness and producing a hazy texture at the same time. That is, the metal acrylate composition with specific content of the heat conductive powder is applied to the resin composition, and can further provide the effects of whitening, removing yellow light and hazing, thereby having good appearance and texture.

On the other hand, examples 19A to 21A and comparative examples 5A and 6A were also groups in which ethylene propylene diene monomer (B1) was used as the unsaturated aliphatic polyolefin (B) but no foaming agent was added, and the composition components thereof were controlled to be the same except for the metal acrylate composition, so that the difference in the results of the groups was estimated to be different from the components of the added metal acrylate composition. As can be seen from the results of examples 19A to 21A and comparative examples 5A and 6A in table 7, the polyolefin elastomers of examples 19A to 21A are significantly improved in the maximum tensile strength as compared with those of comparative examples 5A and 6A to which the metal acrylate composition containing no heat conductive powder was added, thereby showing that the metal acrylate composition containing heat conductive powder of the present invention also has the effect of improving the mechanical strength when applied to the unfoamed resin composition. In addition, the maximum tensile strength test results for examples 19A, 20A and comparative example 5A at three different positions of the test piece were further compared with those of comparative example 5A (106.8 kg/cm, respectively) ² 、83.6kg/cm ² 、127.1kg/cm ² On average 105.8kg/cm ² ) Example 19A (126.2 kg/cm, respectively ² 、116.7kg/cm ² 、123.4kg/cm ² On average 122.1kg/cm ² ) Example 20A (137.1 kg/cm respectively) ² 、137.6kg/cm ² 、132.4kg/cm ² On average 135.7kg/cm ² ) The maximum tensile strength at different positions has higher consistency, and the effect of improving the mechanical strength evenly is shown when the metal acrylate composition containing the heat conducting powder is added.

Test example 7: observation of cell dispersibility of foamed elastomer

The foamed elastomers of example 12A and comparative example 3A were photographed under a magnification of 100 times using a field emission scanning electron microscope (model JOEL JSM-6700F), the results of which are shown in fig. 2A to 2C and fig. 2D to 2F, wherein fig. 2A to 2C correspond to the upper, middle and lower three parts of the foamed elastomer of example 12A, respectively; fig. 2D to 2F correspond to the upper, middle and lower three parts of the foamed elastomer of comparative example 3A, respectively.

As can be seen from fig. 2A to 2C, the foamed elastomer of example 12A has quite similar cell numbers and distribution in the upper, middle and lower three portions, i.e., shows good dispersibility of cells in the foamed elastomer of example 12A; in contrast, in fig. 2D to 2F, the foamed elastomer of comparative example 3A has a significant difference in the number and distribution of cells in the upper, middle and lower three portions, and in particular, the number of cells of fig. 2D is significantly larger than that of fig. 2F, and it is understood that the foamed elastomer of example 12A does have good uniformity of dispersion of cells, that is, by adding a metal acrylate composition containing graphene or flake graphite to a resin composition and making a foamed elastomer, it is possible to improve the uniformity of dispersion of cells in the foamed elastomer.

Claims

1. A metal acrylate composition comprising:

a metal acrylate, which is shown in formula I;

in formula I, M ²⁺ Is zinc ion, magnesium ion or calcium ion, R1 is hydrogen radical or saturated alkyl with 1 to 6 carbon atoms; and

the heat conducting powder is graphene, flake graphite or a combination thereof, wherein the graphene comprises thin-layer reduced graphene oxide with carbon content of more than 60% and number of layers of 3-10 layers and ash value of 0.1-2.5 weight percent or multi-layer reduced graphene oxide with carbon content of more than 60% and number of layers of 10-20 layers and ash value of 0.1-2.5 weight percent; the flake graphite comprises flake graphite with carbon content of more than 95%; the content of the heat conducting powder is 0.3 to 25 weight percent based on the total weight of the acrylic acid metal salt composition.

2. The metal acrylate composition according to claim 1 wherein the thermally conductive powder is present in an amount of 0.3 to 8 weight percent based on the total weight of the metal acrylate composition.

3. The metal acrylate composition according to claim 2 wherein the thermally conductive powder is present in an amount of 0.3 to 2 weight percent based on the total weight of the metal acrylate composition.

4. The metal acrylate composition according to claim 1 wherein the flake graphite comprises flake graphite having a carbon content of 98% or more.

5. A process for the preparation of a metal acrylate composition according to any one of claims 1 to 4 comprising the steps of:

step a): reacting acrylic acid, a divalent metal oxide and a heat conducting powder in a nonpolar solvent at a temperature of 30 ℃ to 100 ℃ to obtain a first mixture; and

step b): removing the solvent from the first mixture to obtain the metal acrylate composition;

wherein the heat conducting powder is graphene, flake graphite or a combination thereof, and the graphene comprises thin-layer reduced graphene oxide with carbon content of above 60% and number of layers of 3-10 layers and ash value of 0.1-2.5 weight percent, or multi-layer reduced graphene oxide with carbon content of above 60% and number of layers of 10-20 layers and ash value of 0.1-2.5 weight percent; the flake graphite comprises flake graphite with carbon content of more than 95%; the content of the heat conducting powder is 0.3 to 25 weight percent based on the total weight of the acrylic acid metal salt composition.

6. The method for producing a metal acrylate composition according to claim 5 wherein the step a) further comprises the steps of:

step a 1): mixing the acrylic acid and the heat conducting powder to obtain a second mixture; and

step a 2): reacting the second mixture and the divalent metal oxide in the nonpolar solvent at a temperature of 30 ℃ to 100 ℃ to obtain the first mixture.

7. The method of claim 5 or 6, wherein the first mixture further comprises an additive comprising an antioxidant, a polymerization inhibitor, a heat-resistant agent, a lubricant, a surfactant, or a combination thereof, and the additive is present in an amount of 0.02 to 10 weight percent based on the total weight of the metal acrylate composition.

8. The method for producing a metal acrylate composition according to claim 5 or 6 wherein the molar ratio of the acrylic acid to the divalent metal oxide is 1.4:1 to 2.1:1.

9. The method for producing a metal acrylate composition according to claim 5 or 6 wherein the nonpolar solvent comprises benzene, toluene, xylene, cyclohexane, hexane, heptane or octane.

10. A resin composition comprising an unsaturated aliphatic polyolefin and a metal acrylate composition according to any one of claims 1 to 4.

11. The resin composition according to claim 10, wherein the metal acrylate composition is used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the unsaturated aliphatic polyolefin.

12. The resin composition of claim 10, wherein the unsaturated aliphatic polyolefin is selected from the group consisting of ethylene propylene diene monomer synthetic rubber, butadiene rubber, butyl rubber, natural rubber, isoprene rubber, and combinations thereof.

13. The resin composition of claim 10, further comprising a copolymer, wherein the copolymer comprises an ethylene copolymer, a polyolefin block copolymer, or a combination thereof.

14. The resin composition of claim 13, wherein the ethylene copolymer is selected from the group consisting of ethylene/vinyl acetate copolymer, ethylene/octene copolymer, polyethylene, ethylene/alpha-olefin copolymer, ethylene/alpha-olefin non-conjugated diene copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/methyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/butyl methacrylate copolymer, and combinations thereof.

15. The resin composition of claim 10, further comprising an organic peroxide, wherein the organic peroxide comprises an alkyl hydroperoxide, a dialkyl hydroperoxide, an aromatic hydroperoxide, a peroxyacid ester, a diperoxide ketal, a diacyl peroxide, or a peroxydicarbonate.

16. The resin composition according to any one of claims 10 to 15, further comprising a foaming agent, wherein the foaming agent comprises an azo compound, a nitroso compound or a sulfonyl hydrazide compound.

17. A polyolefin elastomer prepared from the resin composition according to any one of claims 10 to 15.

18. A foamed elastomer prepared from the resin composition of any one of claims 10 to 16.

19. The foamed elastomer according to claim 18, which is applied to a building material, a vehicle material, a cushioning material, a vibration damping material, a packaging material, a sports pad material or a shoe material.